JPH06192208A - Allophanic acid ester, its preparation and fuel composition for car containing it - Google Patents

Abstract

PURPOSE: To provide the new allophonate esters useful as cleaning agents for gasoline engines especially as agents to prevent depositions on gasoline intake valves or in a fuel chamber.

CONSTITUTION: Alophanate esters of formula I [R is 9-25C alkyl; R¹ is 2-4C oxyalkylene; (m) is 0 or 1; (n) is 5 to 30], e.g. Nnonylphenoxypolyoxypropylene amine of 2-hydorxy-ethane as shown by the formula II. The compounds of formula I are obtained by allowing polyether amines of formula III to react with urea and ethylene carbonate. The compounds of formula I are functional in preventing and removing the depositions on intake valves and in the results lower the necessity of enhancing octane value of gasoline and effective in decreasing the amount of NO. emission. An effective amount of the compounds of the formula I is added to a main ingredients of hydrocarbon fuels having b.p. within the range of gasoline's b.p., thereby obtaining the motor fuel compositions.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention prevents and removes additives for gasoline engine detergents, especially gasoline intake valve deposit (IVD) inhibitors, ie deposits that occur on intake valves. About drugs that help you do. The present invention also reduces combustion chamber deposits and, as a result,
It relates to combustion chamber deposit inhibitors that reduce the need to increase the low octane number of fuels and reduce NO _x emissions.

[0002]

2. Description of the Related Art Combustion of hydrocarbon fuel for an automobile in an internal combustion engine generally causes the formation and accumulation of deposits in various places in the engine combustion chamber, intake valve and exhaust system. The presence of deposits in the combustion chamber significantly reduces the operating efficiency of the engine. First, deposit accumulation in the combustion chamber impedes heat exchange between the combustion chamber and the engine cooling system. Therefore, the combustion chamber temperature becomes higher and the terminal intake air temperature becomes higher. As a result, self-ignition of intake air occurs and engine knocking occurs. In addition, the accumulation of deposits in the combustion chamber reduces the volume of the combustion zone, making the compression ratio of the engine higher than the design value. This also causes engine knock. When the engine knocks, combustion energy is not used effectively. Furthermore, if engine knocking continues for a long time, there is a risk of causing stress fatigue and wear to the engine piston, connecting rod, bearing, and cam rod. The above phenomenon is characteristic of an internal combustion engine using gasoline. This can be suppressed by using high-octane gasoline with knocking resistance to drive the engine, but as the mileage accumulates, higher octane gasoline is required. This phenomenon is known as the engine octane demand increase (ORI) phenomenon. If deposit formation in the combustion chamber of the engine is suppressed or improved and the ORI of the engine is visibly reduced or eliminated, the effect is tremendous.

Another problem common to internal combustion engines is the formation of intake valve deposits, which is a particularly acute problem.
Intake valve deposits prevent valve closure and ultimately lead to poor fuel economy. Such deposits hinder valve movement and valve sealing, cause valve sticking, reduce engine volumetric efficiency, and limit maximum power output. Valve deposits are formed from thermally or oxidatively unstable fuel combustion or lubricating oil oxidation products. The generated hard carbonaceous deposits collect in the pipes and conduits that are components of the exhaust gas recirculation flow (EGR). It is believed that these deposits are formed from exhaust particulates that cool rapidly when mixed with a mixture of air and fuel. When EGR is reduced, causing engine knock and NO _x increase. Therefore, it would be desirable to provide a vehicle fuel that minimizes or does not cause the problem of intake valve deposit formation and the resulting valve sticking.

Currently, an additive for removing deposits, particularly intake valve deposits, is commercially available from Olonite Co., Wilmington, Del., Such as OGA-472 (registered trademark). . However,
These additives lack the ability to remove precipitates, and their efficacy can be improved. Furthermore, polyisobutylene (PI
Detergents based on B) tend to cause the octane number requirement increase phenomenon (ORI).

[0005]

In this way, the deposit is removed from the intake valve of the spark ignition type gasoline engine,
Alternatively, it is an object of the present invention to provide a gasoline additive that prevents the formation of deposits on the intake valve. Another object of the present invention is to provide a gasoline additive that does not promote this action to the formation and accumulation of combustion chamber deposits and therefore does not cause the octane number increase phenomenon (ORI).

[0006]

The present invention provides a class of chemical products useful as gasoline additives containing hydrocarbyl oxide polyether allophane esters of 2-hydroxyethane. This allophanoic acid ester is represented by the following general formula.

[Chemical 3] In the formula, R is a C _{9 to} C ₂₅ alkyl group, and R ¹ is C _{2 to} C ₄
An oxyalkylene group, m is 0 or 1, and n is 5 to 30.
Is the number of.

The present invention also includes (a) a major component which is a hydrocarbon fuel boiling in the gasoline boiling range; and (b) a sufficient amount of a small amount of formula to reduce deposit build-up on intake valves. (1) A fuel for automobiles containing the hydrocarbyl oxide polyether allophane ester of 2-hydroxyethane shown in (1).

The present invention also provides a method of synthesizing the allophane esters of the present invention.

The present inventors have discovered a new class of allophanoic acid esters useful as detergents in automotive fuels. These allophanoic acid ester detergents are now more effective at removing and preventing deposit build-up on inhalation valves than are commercially available detergents.
Further, the allophanic acid ester additive for automotive fuels of the present invention contributes little if any to the octane demand increase phenomenon (ORI) faced by all spark ignition gasoline engines.

The allophane ester of the present invention is represented by the following general formula (1).

[Chemical 4] In the formula, R is a C _{9 to} C ₂₅ alkyl group, and R ¹ is C _{2 to} C ₄
An oxyalkylene group, m is 0 or 1, and n is 5 to 30.
Is the number of. In formula (1), the R group is shown to assume the para position. The R group is sometimes in the ortho position. Therefore, the allophanoic acid ester of the present invention comprises a mixture of both para and ortho isomers. The chemical formula of formula (1) will hereinafter represent both para and ortho isomers, and mixtures of both.

Preferably, R is a C _{9 to} C ₂₁ alkyl group, R ¹ is an oxypropylene group, m is 1 and n is 9 to 15.
Is the number of. In another preferred embodiment, R is C ₉ ~
An alkyl group of C ₂₁ , R ¹ is an oxypropylene group, m is 0, and n is a number of 9 to 15.

More preferably, R is a nonyl group, R ¹ is an oxypropylene group, m is 1 and n is a number of about 12. This more preferable allophanoic acid ester is represented by the following chemical formula.

[Chemical 5]

It should be noted here that the phenyl ring may contain a second nonyl substituent. In this case,
The first nonyl group will take the para position and the second nonyl group will take the ortho position relative to the rest of the molecule.

Synthesis of Allophanoic Acid Esters The allophanoic acid esters of the present invention are the product of the reaction of hydrocarbyloxypolyalkyleneamines with urea and ethylene carbonate.

[0015]

[Chemical 6]

Wherein R is a C ₉ -C ₂₅ alkyl group, R ¹
Oxyalkylene group of C ₂ -C _4, m is 0 or 1,
n is a number of 5 to 30.

The polyetheramine reactant useful in the present invention has the following chemical formula:

[Chemical 7] In the formula, R is a C _{9 to} C ₂₅ alkyl group, and R ¹ is C _{2 to} C ₄
An oxyalkylene group, m is 0 or 1, and n is 5 to 30.
Is the number of. R can be in the para or ortho position.

Preferably, R is a C _{9 to} C ₂₁ alkyl group, R ¹ is an oxypropylene group, m is 1 and n is 9 to 15.
Is the number of. In another preferred embodiment, R is C ₁₂ ~
An alkyl group of C ₂₁ , R ¹ is an oxypropylene group, m is 0, and n is a number of 9 to 15.

As the most preferred polyetheramine,
Nonylphenoxypolyoxypropyleneamine is represented by the following chemical formula.

[Chemical 8]

Nonylphenoxypolyoxypropyleneamine is available from Texaco Chemical Company. It should be noted here that the polyetheramines useful in the present invention may have two nonyl substituents on the phenyl ring. In fact, the commercially available nonylphenoxypolyoxypropyleneamines may contain at least some dinonyl-substituted phenyl ring version of this compound. In this case, the second nonyl group is in the ortho position relative to the body of the molecule.

Ethylene carbonate is commercially available from Texaco Chemical Company.

The allophane ester of the present invention is obtained by the following reaction. In the first step, the polyetheramine with urea is stirred for 6 to 15 hours (preferably about 6 to 15 ° C.) at a temperature of about 130 ° C. while sparging with nitrogen gas to remove the released ammonia.
Heat) After cooling, to remove unreacted urea,
The mixture is filtered. Cooling and filtration are performed as needed.

In the second step, the polyetherurea product of the first step is stirred with ethylene carbonate at a temperature of about 130 ° C. for 6 to 15 hours (preferably about 3).
Heat) The reaction mixture is filtered to remove unreacted material and stripped under reduced pressure at about 80 ° C. for about 1 hour.
The product is the allophane ester of the invention.

The synthesis may be performed in the reverse order. That is,
The ethylene carbonate can be reacted with urea in the first step and the product of this first step can be reacted with the polyetheramine in the second step.

The above-mentioned reaction can be carried out by dissolving all in a hydrocarbon type heavy oil (for example, SNO-600, SNO-850, etc.). Preferably, the reactants are stoichiometric, that is, they use a stoichiometric ratio of 1: 1: 1.

Automotive Fuel Composition The automotive fuel composition of the present invention comprises as a major component greater than 50% by weight a hydrocarbon fuel boiling in the boiling range of gasoline from 32 to about 188 ° C .; and 50% by weight. As a minor component, an allophanoic acid ester is contained in an amount sufficient to reduce deposits on the intake valve.

The preferred automotive base fuel composition is intended for use in a spark ignition internal combustion engine.
Such automotive fuel compositions, commonly referred to as gasoline base stocks, include a mixture of hydrocarbons boiling in the gasoline boiling range, preferably about 32 to about 188 ° C. The base fuel comprises straight or branched chain paraffins, cyclic paraffins, olefins, aromatic hydrocarbons or mixtures thereof. Base fuels include straight run naphtha,
It can be obtained from polymerized gasoline, natural gasoline, catalytically or thermally cracked hydrocarbons, or catalytically reformed feedstocks. The composition and octane number of the base fuel need not be strict, and any ordinary automobile fuel can be used in the practice of the present invention. Furthermore, the fuel composition for motor vehicles can contain any of the additives normally used for gasoline. So the fuel composition is
Anti-knock compounds such as tetraethyl lead, anti-icing additives and the like may be included.

In a broad embodiment of the fuel composition of the present invention, the additive concentration is from about 15 to about 125 PTB (pounds per 1,000 barrels of gasoline base stock). In a preferred embodiment, the concentration of additive composition is about 50-125 PTB. In a more preferred embodiment, the concentration of additive composition is about 80-100 PTB. One PTB corresponds to 2.85 g / m ³ .

The additives of the present invention are SNO-600, SN
Heavy oil such as O-850 or concentration of 30-100 PTB,
It is particularly effective when used with polypropylene glycol (molecular weight 1,000) at a concentration of 65 PTB.

The additives of the present invention are effective at very low concentrations, and therefore, are preferably packaged in diluted form for end-user use. Thus, a diluted form of the additive composition of the present invention may be provided comprising a diluent such as xylene and about 1 to 50% by weight of the additive.

[0031]

EXAMPLES AND EFFECTS OF THE INVENTION The synthesis of the allophanic acid ester of the present invention and the advantages of the present invention will be described in more detail with reference to the following examples.

Example 1 Synthesis of N-nonylphenoxypolyoxypropyleneamine of 2-hydroxyethane 200 g of polyetheramine having a molecular weight of about 1,000
(0.2 mol) with 19.8 g (0.33 mol) of urea,
The reaction was carried out at 130 ° C for 2 hours. 2 hours later, 26.4 g
(0.3 mol) of ethylene carbonate was introduced at 130 ° C., and the reaction was continued at this temperature for 6 hours. The reaction product was hot filtered and then vacuum distilled at 80 ° C. for 2 hours. The final clear product weighed 204.7 g. The following analysis results were obtained. Nitrogen 3.50% by weight TBN 12.78 Molecular weight (by gel phase chromatography) 990

The chemical structure of formula (1) was confirmed by infrared spectroscopy and nuclear magnetic resonance.

Example 2 Intake Valve Cleanliness Retention Test The automotive fuel composition of the present invention is advantageous in reducing intake valve deposit formation. The advantage of the present invention in controlling intake valve deposits is demonstrated by comparing the performance of automotive fuels of the present composition with the performance of automotive fuels containing commercially available detergents. It was

The following fuel composition was subjected to a Honda generator intake valve deposit clean retention test. Fuel A contains 100 PTB of the product of Example 1 as a detergent. Fuel B
Contains the commercially available gasoline additive 60 PTB. The base fuel used for each fuel was a commercially available unleaded gasoline, 45% aromatic, 6% olefin and the balance paraffin. The average calculated octane number of the laboratory price and the car octane number was 87. Boiling point data for the base fuel is shown in Table 1 below.

[0036]

[Table 1]

For the Honda generator test, a Honda generator ES6500 having the following specifications was used.

[0038]

[Table 2]

Each generator was equipped with an automatic throttle controller to maintain a defined speed when loaded. The load was applied by connecting a water heater to each generator. Various loads were simulated by changing the size of the water heater.

The Honda generator test procedure is as follows. The test was started with a new or clean engine (clean valves, manifold, cylinder head, combustion chamber) and freshly injected lubricant. Generator for 80 hours, using test fuel at 1,500W for 2 hours, 2,50
The test cycle of 0 W for 2 hours resulted in 3,60
It was operated at 0 rpm. After that, disassemble the engine, remove the seal with the valve spring attached, and leave it at -18
Stored in freezer at 0 ° F.

Intake Valve Adhesion Test The effort required by a trained evaluator to manually push open the intake valve was quantified. Efforts have been linked to the problem of valve sticking in cars. That is, a valve that could not be pushed open by hand was generally associated with a cold start problem for a vehicle.

CRC Intake Valve Test Each component of the intake system (valve, manifold, cylinder head) and combustion chamber was tested with a standard Research Coordination Council (CR
C) Visually assessed by the test procedure (1 to 10 scale, 1 fouling, 10 clean). The performance of the test fuel was measured in part by the cleanliness of the intake system components.

Fuel A and fuel B were subjected to this Honda generator intake valve cleanliness retention test. The results are summarized in Table 3.

[0044]

[Table 3]

Fuel A, a gasoline with the additive of the present invention, showed very good results in the CRC valve test. The intake valve has virtually no precipitate (13
mg or less), and no stickiness was observed. On the other hand, Fuel B containing a commercially available gasoline additive gave poor results in the CRC valve test and also gave 269 mg of intake valve deposits. Therefore, the allophanic acid ester according to the present invention exhibited extremely excellent detergency and retention characteristics of the intake valve cleanliness.

Example 3 Thermogravimetric Analysis (TGA) In order to determine whether the sample of the allophanoic acid ester of Example 1 would increase deposits in the combustion chamber, the pyrolysis rate was determined using the TGA method. Analyzed. The procedure used is the chevron test method, which rapidly heats the additive compound in air and measures its volatility at 200 ° C and 295 ° C. The test method is described more clearly as follows. Sample at 200 ℃
Heat to. Hold at this temperature for 30 minutes, then 295 ° C
Heat to. Hold at this temperature for a further 30 minutes. The weight of the sample (initially about 20 mg) is recorded at the start, after the first heating period and after the last heating period. From start to 200 ° C, and 200 ° C to 295 ° C
The weight difference up to is recorded and the percent loss, or volatility, is calculated (final weight at 295 ° C is also
Considered as a residue). The heating is done in an air flow of 60 ml / min.

The following results were obtained.

[0048]

[Table 4]

The test results of trial 1 and trial 2 show that 90% of the additives of the present invention were thermally decomposed at 295 ° C.
While volatile, it was shown to be only 62.8% for derivatives containing PIB such as OGA-472. These results indicate that the additive of the present invention leaves only a small amount of combustion chamber deposits in actual engine operation and, therefore, does not contribute to Octane Demand Increase (ORI).

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[Procedure amendment]

[Submission date] December 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction content]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention prevents and removes additives for gasoline engine detergents, especially gasoline intake valve deposit (IVD) inhibitors, ie deposits that occur on intake valves. About drugs that help you do. The present invention also reduces combustion chamber deposits and, as a result,
It relates to combustion chamber deposit inhibitors that reduce the need to increase the octane number of fuels and reduce NO _x emissions.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

In the second step, the polyetherurea product of the first step is stirred with ethylene carbonate at a temperature of about 130 ° C. for 1 to 15 hours (preferably about 3).
Heat) The reaction mixture is filtered to remove unreacted material and stripped under reduced pressure at about 80 ° C. for about 1 hour.
The product is the allophane ester of the invention.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Automotive Fuel Composition The automotive fuel composition of the present invention comprises as a main component in excess of 50% by weight a hydrocarbon fuel boiling in the gasoline boiling range of 32 to 188 ° C .; less than 50% by weight. As a sub-component of the above, it contains a sufficient amount of allophanoic acid ester to reduce the deposit on the intake valve.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

The chemical structure of formula (1) was confirmed by infrared spectroscopy and nuclear magnetic resonance. The infrared absorption spectrum and ¹³ C nuclear magnetic resonance spectrum are shown in FIGS. 1 and 2.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 is a chart of infrared absorption spectrum of the product obtained in Example 1.

FIG. 2 is a ¹³ C nuclear magnetic resonance spectrum of the product obtained in Example 1.

[Procedure correction 6]

[Document name to be corrected] Drawing

[Correction target item name] All drawings

[Correction method] Change

[Correction content]

[Figure 1]

[Fig. 2]

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Constance Annette Cadorette New York 12550, Newberg, Little Briton Road, USA 323

Claims (3)

[Claims] 1. A general formula: (In the formula, R is a C _{9 to} C ₂₅ alkyl group, and R ¹ is C ₂ to C.
₄ oxyalkylene group, m is 0 or 1, n is 5 to 3
An allophane ester represented by the number 0). 2. A small amount of allophane according to claim 1, which is (a) a major component which is a hydrocarbon fuel boiling in the gasoline boiling range; and (b) a sufficient amount to reduce deposit build-up on intake valves. An automotive fuel composition containing an acid ester. 3. A general formula: (In the formula, R is a C _{9 to} C ₂₅ alkyl group, and R ¹ is C ₂ to C.
₄ oxyalkylene group, m is 0 or 1, n is 5 to 3
A method for producing an allophanoic acid ester, which comprises reacting a polyetheramine represented by a number of 0) with urea and ethylene carbonate.